US10987899B2 - Active energy ray curable resin composition, laminate, manufacturing method thereof, and product - Google Patents

Active energy ray curable resin composition, laminate, manufacturing method thereof, and product Download PDF

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Publication number
US10987899B2
US10987899B2 US16/129,189 US201816129189A US10987899B2 US 10987899 B2 US10987899 B2 US 10987899B2 US 201816129189 A US201816129189 A US 201816129189A US 10987899 B2 US10987899 B2 US 10987899B2
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resin composition
active energy
curable resin
ray curable
energy ray
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US20190094423A1 (en
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Ryo Suzuki
Shinobu Hara
Mikihisa Mizuno
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Dexerials Corp
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Dexerials Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G1/00—Mirrors; Picture frames or the like, e.g. provided with heating, lighting or ventilating means
    • A47G1/02—Mirrors used as equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/002—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising natural stone or artificial stone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/147—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

  • the present invention relates to a laminate, a manufacturing method of the laminate, a product using the laminate, and an active energy ray curable resin composition.
  • the laminate can be used in a wide variety of fields (building use, industrial use, automobile use, optical use, solar battery panels, etc.) and the laminate has at least one of an anti-fogging property and an anti-fouling property.
  • the active energy ray curable resin composition can be applicable for formation of a primer layer of the laminate.
  • an anti-fogging treatment or an anti-fouling treatment is applied to the resin films and glass.
  • an electron ray curable hard coat sheet having an anti-fogging property and an anti-fouling property, and having a certain composition (see, for example, Japanese Patent No. 3760669).
  • a method for manufacturing any of these laminates is typically a method where a resin composition having an anti-fogging property or an anti-fouling property is applied onto a substrate and then the resin composition is cured to form a functional layer having an anti-fogging property or an anti-fouling property, to thereby obtain a laminate.
  • a primer layer may be formed between the substrate and the functional layer to improve adhesion between the substrate and the functional layer. In this case, there are problems that a transmission image or reflection image of the laminate is distorted on an edge portion of the laminate to degrade visibility of the image.
  • the present invention aims to solve the above-described various problems existing in the art and to achieve the following object. Namely, the present invention has an object to provide a laminate having excellent visibility on an edge portion thereof, where the laminate includes a primer layer and has at least one of an anti-fogging property and an anti-fouling property, a manufacturing method of the laminate, a product using the laminate, and an active energy ray curable resin applicable for formation of the primer layer of the laminate.
  • a laminate including:
  • a functional layer disposed on the primer layer, where the functional layer has a function of at least one of an anti-fogging property and an anti-fouling property, wherein a surface of an edge portion of the laminate at the side of the functional layer has a projected portion having an apex formed along an edge side of the edge portion, and
  • a height of the projected portion is 10 ⁇ m or less, a width of the projected portion is 15 mm or less, and a length between the edge side and the apex is 5.0 mm or less.
  • a height of the projected portion is from 1 ⁇ m to 10 ⁇ m.
  • a surface of the functional layer has a pure water contact angle of 80° or more and a hexadecane contact angle of 35° or more.
  • ⁇ 4> The laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the primer layer has an average thickness of from 0.5 ⁇ m to 5 ⁇ m.
  • ⁇ 5> The laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the functional layer has an average thickness of 10 ⁇ m or more.
  • ⁇ 6> The laminate according to any one of ⁇ 1> to ⁇ 5>, wherein the functional layer has a coefficient of dynamic friction of 0.40 or less.
  • ⁇ 7> The laminate according to any one of ⁇ 1> to ⁇ 6>, wherein the primer layer is a cured product of an active energy ray curable resin composition, and the active energy ray curable resin composition includes a surfactant.
  • ⁇ 8> The laminate according to ⁇ 7>, wherein the surfactant is at least one of a silicone-based surfactant and a fluorine-based surfactant.
  • an amount of the surfactant in the active energy ray curable resin composition is from 0.0001% by mass to 5.0% by mass relative to a non-volatile component of the active energy ray curable resin composition.
  • the laminate according to any one of ⁇ 1> to ⁇ 9> on a surface of the product.
  • the product is at least one of a mirror for bathrooms, and a mirror for washstands.
  • An active energy ray curable resin composition including:
  • active energy ray curable resin composition is used for forming the primer layer of the laminate according to any one of ⁇ 1> to ⁇ 6>.
  • the surfactant is at least one of a silicone-based surfactant and a fluorine-based surfactant.
  • an amount of the surfactant in the active energy ray curable resin composition is from 0.0001% by mass to 5.0% by mass relative to a non-volatile component of the active energy ray curable resin composition.
  • an active energy ray curable resin composition including a surfactant onto the substrate and curing the active energy ray curable resin composition to form the primer layer.
  • the surfactant is at least one of a silicone-based surfactant and a fluorine-based surfactant.
  • an amount of the surfactant in the active energy ray curable resin composition is from 0.0001% by mass to 5.0% by mass relative to a non-volatile component of the active energy ray curable resin composition.
  • the present invention can solve the above-described various problems existing in the art, achieve the above-mentioned object, and can provide a laminate having excellent visibility on an edge portion thereof, where the laminate includes a primer layer and has at least one of an anti-fogging property and an anti-fouling property, a manufacturing method of the laminate, a product using the laminate, and an active energy ray curable resin applicable for formation of the primer layer of the laminate.
  • FIG. 1 is a schematic view illustrating one example of a cross-section profile of a laminate
  • FIG. 2 is a schematic cross-sectional view illustrating one example of the laminate of the present invention
  • FIG. 3 is a schematic cross-sectional view illustrating one example of a product of the present invention.
  • FIG. 4A is a schematic view explaining a method of an anti-fogging test using vapor.
  • FIG. 4B is a schematic view explaining the method of an anti-fogging test using vapor.
  • a laminate of the present invention includes at least a substrate, a primer layer, and a functional layer.
  • the laminate may further include other members according to the necessity.
  • a functional layer having a function such as an anti-fogging property and an anti-fouling property
  • a functional layer having a function such as an anti-fogging property and an anti-fouling property
  • an image is distorted on an edge portion of a laminate to degrade visibility.
  • a reduction in visibility becomes more significant, as an average thickness of the functional layer is thicker (for example, an average thickness is 10 ⁇ m or more).
  • the present inventors diligently conducted researches to solve the above-mentioned problem. Then, the present inventors confirmed that a cause for degrading visibility was a projected portion formed on an edge portion. Moreover, the present inventors confirmed that, when the functional layer was formed by a coating method, a coating material applied onto an edge portion of the substrate was risen due to a surface tension to form a projected portion on the edge portion.
  • the present inventors diligently conducted further researches and found that formation of a projected portion on an edge portion could be suppressed by adding a surfactant to a composition used for forming a primer layer. As a result, the present invention was accomplished.
  • the laminate has the following characteristics.
  • the laminates includes the primer layer and the functional layer.
  • a surface of an edge portion of the laminate at the side of the functional layer has a projected portion having an apex formed along an edge side of the edge portion.
  • a height of the projected portion is 10 ⁇ m or less, a width of the projected portion is 15 mm or less, and a length between the edge side and the apex is 5.0 mm or less.
  • edge portion means a region including an edge side and an area near the edge side as well as including the edge side itself.
  • each length of the cross-section can be determined, for example, by measuring a cross-section profile of the laminate.
  • FIG. 1 One example of a cross-section profile is illustrated in FIG. 1 .
  • FIG. 1 is a schematic view illustrating one example of the cross-section profile.
  • FIG. 1 is a schematic view illustrating a profile of a cross-section orthogonal to a direction of an edge side of the laminate and to a planar direction of a surface of the laminate at the side of the functional layer.
  • the solid line (f) having a projected portion depicts a surface of the functional layer.
  • the referential sign (t) depicts a top of a peak (apex), the referential sign (a) depicts an edge side, the referential sign (h) depicts a height of the peak, the referential sign (w) depicts a width of the peak, and the referential sign (l) depicts a horizontal distance between the edge side (a) and the top (t) of the peak (a length between the edge side and the apex).
  • the height (h) of the peak is a distance from the apex (t) to an extended line (i) of the horizontal surface (f 1 ) of the surface of the laminate at the side of the functional layer.
  • the width (w) of the projected portion is a distance from a bottom edge (f 2 ) of the projected portion at the center side of the surface to a line (ii) orthogonal to the surface of the laminate at the side of functional layer.
  • the horizontal distance (l) is a distance between the line (ii) and a vertical line drawn on the extended line (i) from the apex (t).
  • a position of a top of a projected portion is important. Visibility is poor when the top is too far from the edge side even when a height and width of a projected portion are small.
  • the conditions for achieving good visibility includes all of the following (1) to (3).
  • a height of the projected portion [height (h) of the peak] is 10 ⁇ m or less.
  • a width (w) of the projected portion is 15 mm or less.
  • a length between the edge side and the apex [horizontal distance (l)] is 5.0 mm or less.
  • the height of the projected portion is more than 10 ⁇ m, distortion of an image is significantly visually recognized due to refraction. Therefore, deterioration of visibility cannot be prevented unless the height of the projected portion satisfies (1) above, even though the width of the projected portion and the length between the edge side and the apex satisfy (2) and (3), respectively.
  • a width of distortion of an image visually observed length from the edge side to an area where distortion of the image disappears towards a center direction.
  • the width of the projected portion is more than 15 mm
  • the height of the projected portion is 10 ⁇ m or less, preferably 8.0 ⁇ m or less, more preferably 7.0 ⁇ m or less, and particularly preferably 6.5 mm or less.
  • the lower limit of the height of the projected portion is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the height of the projected portion may be 1.0 ⁇ m or more, 2.0 ⁇ m or more, or 4.0 ⁇ m or more.
  • the width of the projected portion is 15 mm or less, preferably 14 mm or less, more preferably 10 mm or less, and particularly preferably 6.0 mm or less.
  • the lower limit of the width of the projected portion is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the width of the projected portion may be 1.0 mm or more, 3.0 mm or more, or 5.0 mm or more.
  • the length (length between the edge side and the apex) is 5.0 mm or less, preferably 4.5 mm or less, more preferably 3.5 mm or less, and particularly preferably 3.0 mm.
  • the lower limit of the length is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the length may be 0.5 mm or more, 1.0 mm or more, or 2.0 mm or more.
  • the height of the projected portion is particularly preferably 5.5 mm or less
  • the width of the projected portion is particularly preferably 6.0 mm or less
  • the length (length between the edge side and the apex) is particularly preferably 3.0 mm or less.
  • a cross-section profile of the laminate can be measured, for example, by the following method.
  • a cross-section profile of a surface of the edge portion is measured by means of Stylus Surface Profilometer P-15 available from KLA-Tencor under the following conditions.
  • the substrate is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples of the substrate include a resin substrate and an inorganic substrate.
  • Examples of the inorganic substrate include a glass substrate, a quartz substrate, and a sapphire substrate.
  • the glass substrate is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples of the glass substrate include silica glass (silicate glass), soda-lime glass, and potash glass.
  • the glass substrate may be tempered glass, laminated glass, or heat-resistant glass.
  • the glass substrate may be used in any application, such as windowpanes for automobiles, windowpanes for buildings, lens, mirrors, and goggles.
  • a shape of the glass substrate is typically a plate shape, but the glass substrate may have any shape, such as a sheet shape and a curved shape.
  • a material of the resin substrate is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the material include triacetyl cellulose (TAC), polyester (TPEE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyamide (PA), aramid, polyethylene (PE), polyacrylate, polyether sulfone, polysulfone, polypropylene (PP), polystyrene, diacetyl cellulose, polyvinyl chloride, an acrylic resin (PMMA), polycarbonate (PC), an epoxy resin, a urea resin, a urethane resin, a melamine resin, a phenol resin, an acrylonitrile-butadiene-styrene copolymer, a cycloolefin polymer (COP), a cycloolefin copolymer (COC), a PC/PMMA laminate, and rubber-added PMMA.
  • TAC triacetyl
  • the substrate is preferably transparent.
  • a form of the substrate is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the form of the substrate is preferably a film.
  • an average thickness of the substrate is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the average thickness is preferably from 5 ⁇ m to 1,000 ⁇ m and more preferably from 50 ⁇ m to 500 ⁇ m.
  • a binder layer may be disposed in order to increase close adhesiveness between the substrate and a fabrication material during fabrication of the laminate, or in order to protect the letters, patterns, and images from flow resistive pressure of the fabrication material during fabrication of the laminate.
  • any of various binders such as acryl-based binders, urethane-based binders, polyester-based binders, polyamide-based binders, ethylene butyl alcohol-based binders, and ethylene-vinyl acetate copolymer-based binders, and various adhesives can be used.
  • two or more binder layers may be disposed as the binder layer.
  • a binder having heat-sensitivity and pressure-sensitivity suitable for a fabrication material can be selected.
  • a surface of the substrate opposite to the side of the functional layer may have a wrinkle pattern. Since the wrinkle pattern is disposed, blocking is prevented when a plurality of the laminates are stacked, handling in subsequent steps are improved, and products can be efficiently manufactured.
  • the wrinkle pattern can be formed by surface texturing.
  • blocking means a phenomenon that sheets are difficult to peel away from each other when a plurality of sheets are stacked.
  • the functional layer may not have sufficient adhesion to the substrate.
  • a primer layer configured to improve adhesion of the functional layer to the substrate is disposed between the substrate and the functional layer.
  • an average thickness of the primer layer is preferably 0.5 ⁇ m or more.
  • the average thickness of the primer layer is preferably from 0.5 ⁇ m to 20 ⁇ m, even more preferably from 0.5 ⁇ m to 10 ⁇ m, and particularly preferably from 0.5 ⁇ m to 5 ⁇ m.
  • the average thickness of the primer layer is within the preferable range, adhesion is unlikely to be reduced even when the primer layer is exposed to high-temperature vapor (e.g., 60° C. or higher), thermal impact (e.g., a significant change from ⁇ 20° C. to 80° C.), or an alkaline detergent and peeling of the functional layer can be prevented.
  • high-temperature vapor e.g., 60° C. or higher
  • thermal impact e.g., a significant change from ⁇ 20° C. to 80° C.
  • an alkaline detergent and peeling of the functional layer can be prevented.
  • the average thickness can be determined by the following method.
  • a thickness of the primer layer can be measured by observing a cross-section of the laminate under a field emission scanning electron microscope S-4700 (product name, available from Hitachi High-Technologies Corporation). The thickness is measured at randomly selected 10 points. An average value of the measured values is determined as an average thickness. In this case, the measurement is performed at points excluding the edge portion of the laminate.
  • the primer layer can be formed by applying an active energy ray curable resin composition.
  • the primer layer is a cured product obtained, for example, by curing an active energy ray curable resin composition with active energy rays.
  • the active energy ray curable resin composition includes a surfactant, and may further include other components, such as urethane (meth)acrylate, a photopolymerization initiator, and a solvent, according to the necessity.
  • the active energy ray curable resin composition includes the surfactant, a height of a projected portion at an edge of a primer layer to be obtained, a width of the projected portion, and a length between an edge side and an apex are kept small. As a result, a height of a projected portion at an edge portion of a functional layer to be formed on the primer layer, a width of the projected portion, and a length between an edge side and an apex can be made small.
  • surfactant examples include silicone-based surfactants, acryl-based surfactants, cation-based surfactants, anion-based surfactants, nonion-based surfactants, amphoteric surfactants, and fluorine-based surfactants.
  • silicone-based surfactants acryl-based surfactants, cation-based surfactants, anion-based surfactants, nonion-based surfactants, amphoteric surfactants, and fluorine-based surfactants.
  • a silicone-based surfactant is preferable because surface tension can be significantly reduced.
  • modified silicone such as polyester-modified silicone and polyether-modified silicone
  • polyether-modified silicone is preferable because surface tension can be significantly reduced.
  • polyether-modified silicone polyether-modified polydimethylsiloxane is preferably used.
  • polyester-modified silicone polyester-modified polydimethylsiloxane is preferably used.
  • Examples of commercial products of the silicone-based surfactant include BYK-347, BYK-348, BYK-UV3500, BYK-UV3510, BYK-UV3530, and BYK-UV3570 (all product names, available from BYK) and KP323 (product name, available from Shin-Etsu Chemical Co., Ltd.).
  • BYK-UV3500, BYK-UV3510, and KP323 are preferable because wettability of a composition (coating material) for forming the functional layer becomes even more excellent.
  • fluorine-based surfactant examples include a fluorine-based surfactant having a structure including a perfluoroalkyl group.
  • Examples of commercial products of the fluorine-based surfactant include: MAGAFACE F-470, F-471, F-472SF, F-474, F-475, R-30, F-477, F-478, F-479, BL-20, R-61, and R-90 (all product names, available from DIC Corporation); and FC-170C, FC-4430, and FC-4432 (all product names, available from Sumitomo 3M Limited).
  • the surfactant may or may not have a (meth)acryloyl group.
  • An amount of the surfactant in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.
  • An amount of the surfactant is preferably from 0.0001% by mass to 5.0% by mass, more preferably from 0.0001% by mass to 3.0% by mass, and particularly preferably from 0.005% by mass to 1.0% by mass relative to a non-volatile component of the active energy ray curable resin composition.
  • the amount is within the particularly preferable range, both adhesion and reduced surface tension are achieved at a high level.
  • the urethane (meth)acrylate is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples of the urethane (meth)acrylate include aliphatic urethane (meth)acrylate and aromatic urethane (meth)acrylate. Among the above-listed examples, aliphatic urethane (meth)acrylate is preferable.
  • An amount of the urethane (meth)acrylate in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the amount of the urethane (meth)acrylate is preferably from 40% by mass to 80% by mass, more preferably from 50% by mass to 75% by mass, and particularly preferably from 60% by mass to 70% by mass, relative to a non-volatile component of the active energy ray curable resin composition.
  • photopolymerization initiator examples include specific examples of the photopolymerization initiator listed in the description of the functional layer described later.
  • Specific examples of the solvent include specific examples of the solvent listed in the description of the functional layer described layer.
  • the active energy ray curable resin composition preferably further includes (meth)acrylate having an alkylene oxide structure.
  • the (meth)acrylate having an alkylene oxide structure include glycerin alkoxytri(meth)acrylate, pentaerythritol alkoxytetra(meth)acrylate, isocyanuric acid alkoxytri(meth)acrylate, bisphenol A alkoxydi(meth)acrylate, polyalkylene glycol di(meth)acrylate, and trimethylol propane alkoxytri(meth)acrylate.
  • the alkylene oxide include ethylene oxide and propylene oxide.
  • An amount of the (meth)acrylate having an alkylene oxide structure in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the amount of the (meth)acrylate having an alkylene oxide structure is preferably from 15% by mass to 50% by mass, more preferably from 20% by mass to 45% by mass, and particularly preferably from 25% by mass to 38% by mass, relative to a non-volatile component of the active energy ray curable resin composition.
  • a method of the coating is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples of the method include wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating, microgravure coating, lip coating, air knife coating, curtain coating, comma coating, and dip coating.
  • the active energy ray curable resin composition is cured by radiation of active energy rays.
  • the active energy rays are not particularly limited and may be appropriately selected depending on the intended purpose. Examples of the active energy rays include electron beams, UV rays, infrared rays, laser beams, visible rays, ionizing radiation (X rays, ⁇ rays, ß rays, ⁇ rays, etc.), microwaves, and high-frequency waves.
  • the functional layer has at least one of an anti-fogging property and an anti-fouling property.
  • a pure water contact angle of a surface of the functional layer is preferably 80° or more, more preferably 90° or more, and particularly preferably 100° or more.
  • the upper limit of the pure water contact angle is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the pure water contact angle may be 130° or less, 150° or less, or 170° or less.
  • the pure water contact angle is measured using a contact angle meter, PCA-1 (available from Kyowa Interface Science Co., Ltd.) under the following conditions. Distilled water is placed in a plastic syringe. To the tip of the syringe, a stainless steel needle is attached. The distilled water is allowed to drip on an evaluation surface (surface of the functional layer).
  • PCA-1 available from Kyowa Interface Science Co., Ltd.
  • the contact angle 5 seconds after dripping of water is measured at randomly selected 10 points on the surface of the functional layer, and the average value thereof is determined as the pure water contact angle.
  • a hexadecane contact angle of a surface of the functional layer is preferably 35° or more, more preferably 40° or more, and particularly preferably 60° or more.
  • the upper limit of the hexadecane contact angle is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the hexadecane contact angle may be 100° or less, 120° or less, or 150° or less.
  • the hexadecane contact angle is measured using a contact angle meter, PCA-1 (available from Kyowa Interface Science Co., Ltd.) under the following conditions. Hexadecane is placed in a plastic syringe. To the tip of the syringe, a stainless steel needle is attached. The hexadecane is allowed to drip on an evaluation surface (surface of the functional layer).
  • PCA-1 available from Kyowa Interface Science Co., Ltd.
  • Amount of hexadecane to be dripped 1 ⁇ L
  • the contact angle 20 seconds after dripping of hexadecane is measured at randomly selected 10 points on the surface of the functional layer, and the average value thereof is determined as the hexadecane contact angle.
  • the pure water contact angle falls within the above-mentioned preferable range and the hexadecane contact angle falls within the above-mentioned preferable range, it is possible to prevent stains from permeating into an underlying layer of a bulk even if aqueous stains and/or oily stains (e.g., ink of felt pens, finger prints, sweat, and cosmetics such as foundation cosmetics and UV protectors) are adhered to the surface of the functional layer. Therefore, the functional layer excels in an anti-fouling property in addition to the anti-fogging property.
  • aqueous stains and/or oily stains e.g., ink of felt pens, finger prints, sweat, and cosmetics such as foundation cosmetics and UV protectors
  • a coefficient of dynamic friction of the functional layer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the coefficient of dynamic friction thereof is preferably 0.40 or less, more preferably 0.37 or less, and particularly preferably 0.30 or less.
  • the coefficient of dynamic friction is 0.40 or less, slidability of a wiping material is good and dirt that may be deposited is easily wiped. Moreover, an effect of releasing a force is obtained and therefore the functional layer is unlikely to be scratched.
  • the lower limit of the coefficient of dynamic friction of the functional layer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the coefficient of dynamic friction of the functional layer is preferably 0.10 or more.
  • the coefficient of dynamic friction is determined by the following method.
  • the coefficient of dynamic friction is measured using Triboster TS501 (product name, available from Kyowa Interface Science Co., Ltd.).
  • BEMCOT registered trademark
  • M-3II product name, available from by Asahi Kasei Corporation
  • the coefficient of dynamic friction is measured at randomly selected 12 points at a measuring load of 50 g/cm 2 , a measuring speed of 1.7 mm/s, and a measuring distance of 20 mm, and the average value thereof is determined as the coefficient of dynamic friction.
  • a thickness of the functional layer In order to prevent fogging in a high-temperature and high-humidity (e.g., 35° C. and 85% RH) atmosphere for a certain period or longer (e.g., 10 minutes or longer), it is effective to adjust a thickness of the functional layer to a certain thickness or thicker.
  • a high-temperature and high-humidity e.g., 35° C. and 85% RH
  • an average thickness of the functional layer is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and particularly preferably 30 ⁇ m or more.
  • the average thickness of the functional layer is thick, a height of the projected portion of the edge portion becomes high by the thickness of the functional layer. Therefore, the average thickness is preferably less than 45 ⁇ m and more preferably 40 ⁇ m or less.
  • the average thickness can be determined by the following method.
  • a thickness of the functional layer can be measured by observing a cross-section of the laminate under a field emission scanning electron microscope S-4700 (product name, available from Hitachi High-Technologies Corporation). The thickness is measured at randomly selected 10 points. An average value of the measured values is determined as an average thickness. In this case, the measurement is performed at points excluding the edge portion of the laminate.
  • the functional layer is a cured product of an active energy ray curable resin composition.
  • the active energy ray curable resin composition preferably includes a hydrophobic monomer having a hydrophobic molecular structure and a surfactant.
  • the active energy ray curable resin may further include other monomers, a polymerization initiator, a solvent, etc., according to the necessity.
  • the hydrophobic monomer has a hydrophobic molecular structure.
  • examples of the hydrophobic molecular structure include a structure including fluorine or silicon.
  • examples of the hydrophobic molecular structure include a fluoroalkyl structure, a perfluoropolyether structure, and a dimethylsiloxane structure.
  • the hydrophobic monomer is preferably (meth)acrylate including a perfluoropolyether group and is preferably a compound including, as a perfluoropolyether group, a repeating structure of —(O—CF 2 CF 2 )—, —(O—CF 2 CF 2 CF 2 )—, or —(O—CF 2 C(CF 3 )F)—.
  • hydrophobic monomer examples include DAC-HP available from DAIKIN INDUSTRIES, LTD., FLUOROLINK AD1700 available from Solvay Specialty Polymers Japan K.K., FLUOROLINK MD700 available from Solvay Specialty Polymers Japan K.K., CN4000 available from Sartomer, and KY-1203 available from Shin-Etsu Chemical Co., Ltd.
  • the hydrophobic monomer has a perfluoropolyether group (perfluoropolyether structure)
  • the functional layer has low surface energy
  • dirt on a resultant functional layer is easily wiped because a molecular chain thereof is flexible and easily moved.
  • the hydrophobic monomer preferably has a perfluoropolyether group (perfluoropolyether structure).
  • the hydrophobic monomer is (meth)acrylate.
  • the hydrophobic monomer is, for example, (meth)acrylate having a hydrophobic molecular structure.
  • An amount of the hydrophobic monomer in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the amount of the hydrophobic monomer is preferably from 0.001% by mass to 10% by mass, more preferably from 0.001% by mass to 5.0% by mass, and particularly preferably from 0.01% by mass to 5.0% by mass, relative to a total amount of monomers in the active energy ray curable resin composition.
  • the surfactant is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the details and preferable embodiments of the surfactant are identical to the details and preferable embodiments of the surfactant as a component of the active energy ray curable resin composition in the description of the primer layer.
  • the active energy ray curable resin composition for forming the functional layer includes the surfactant as well as the active energy ray curable resin composition for forming the primer layer including the surfactant, a height of a projected portion on an edge portion of the functional layer formed on the primer layer, a width of the projected portion, and a length between the edge side and the apex can be made even smaller.
  • An amount of the surfactant in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the amount of the surfactant is preferably from 0.0001% by mass to 5.0% by mass, more preferably from 0.0001% by mass to 3.0% by mass, and particularly preferably from 0.005% by mass to 1.0% by mass, relative to a non-volatile component of the active energy ray curable resin composition.
  • Examples of the above-mentioned other monomers include a hydrophilic monomer and a crosslinking agent.
  • the hydrophilic monomer has an alkylene oxide equivalent of less than 100 and an acryl equivalent of from 200 to 500.
  • the alkylene oxide equivalent is a monomer mass per mole of an alkylene oxide group and is obtained by dividing a molecular weight of the monomer with the number of alkylene oxide groups per mole of the monomer.
  • the acryl equivalent is a monomer mass per mole of a (meth)acryl group and is obtained by dividing a molecular weight of a monomer with the number of (meth)acryl groups [also referred to as (meth)acryloyl groups] per molecule of the monomer.
  • the number of carbon atoms of an alkylene group in the alkylene oxide is preferably from 1 to 12, and more preferably from 1 to 4.
  • alkylene oxide examples include methylene oxide (the number of carbon atoms: 1), 1,2-ethyleneoxide (the number of carbon atoms: 2), 1,3-propyleneoxide (the number of carbon atoms: 3), 1,2-propyleneoxide (the number of carbon atoms: 3), and 1,4-butyleneoxide (the number of carbon atoms: 4).
  • the lower limit of the alkylene oxide equivalent of the hydrophilic monomer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the alkylene oxide equivalent is, for example, 30 or greater, 40 or greater, etc.
  • the hydrophilic monomer includes a (meth)acryloyl group.
  • the number of the (meth)acryloyl groups in the hydrophilic monomer is not particularly limited and may be appropriately selected depending on the intended purpose. The number is preferably from 2 to 6 and more preferably from 2 to 4.
  • (meth)acryloyl group means an acryloyl group or a methacryloyl group.
  • the hydrophilic monomer is not particularly limited and may be appropriately selected depending on the intended purpose, as long as the hydrophilic monomer has an alkylene oxide equivalent of less than 100 and an acryl equivalent of from 200 to 500.
  • the hydrophilic monomer include alkoxylated trimethylol propane tri(meth)acrylate, alkoxylated glycerin tri(meth)acrylate, alkoxylated pentaerythritol tetra(meth)acrylate, and polyalkylene glycol di(meth)acrylate.
  • alkoxylated trimethylol propane tri(meth)acrylate include ethoxylated trimethylol propane tri(meth)acrylate.
  • a molecular weight of the hydrophilic monomer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the molecular weight thereof is preferably from 300 to 2,500, more preferably from 400 to 2,000, and particularly preferably from 600 to 1,500.
  • An amount of the hydrophilic monomer in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the amount of the hydrophilic monomer is preferably from 55% by mass to 90% by mass and more preferably from 60% by mass to 75% by mass relative to a non-volatile component of the active energy ray curable resin composition. When the amount falls within the above-mentioned preferable range, the functional layer is unlikely to fog, to be scratched, and to be affected by chemicals.
  • the crosslinking agent is different from the hydrophilic monomer.
  • the crosslinking agent has an alkylene oxide equivalent of 100 or more.
  • the crosslinking agent moreover has an acryl equivalent of less than 400.
  • crosslinking agent that does not have alkylene oxide is also included in the crosslinking agent.
  • the crosslinking agent is a non-alicyclic crosslinking agent. Namely, the crosslinking agent does not have an alicyclic structure.
  • the alicyclic structure is a ring structure composed of 3 or more carbon atoms.
  • alkylene oxide examples include ethylene oxide and 1,2-propyleneoxide.
  • the lower limit of the acryl equivalent of the crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples of the acryl equivalent include 100 or more.
  • the crosslinking agent includes a (meth)acryloyl group.
  • the number of the (meth)acryloyl groups in the crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. The number thereof is preferably from 2 to 6.
  • the crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose, as long as an alkylene oxide equivalent thereof is 100 or more and an acryl equivalent thereof is less than 400.
  • examples of the crosslinking agent include pentaerythritol alkoxytetra(meth)acrylate, aliphatic urethane (urethane)acrylate, and ethoxylated bisphenol A diacrylate.
  • a molecular weight of the crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the molecular weight thereof is preferably from 300 to 2,500, more preferably from 400 to 2,000, and particularly preferably from 500 to 1,900.
  • An amount of the crosslinking agent in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the amount of the crosslinking agent is preferably from 5% by mass to 40% by mass, more preferably from 20% by mass to 35% by mass, and particularly preferably from 20% by mass to 30% by mass relative to a non-volatile component of the active energy ray curable resin composition.
  • the amount thereof is less than 5% by mass, scratch resistance and chemical resistance are impaired.
  • an anti-fogging property may be degraded.
  • AO denotes alkylene oxide
  • (15) means that the average number of ethylene oxide groups included per mole is 15.
  • Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photo-acid generating agent, a bisazide compound, hexamethoxymethylmelamine, and tetramethoxy glycoluril.
  • the photoradical polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples of the photoradical polymerization initiator include the following compounds.
  • the photopolymerization initiator is preferably from free from a nitrogen atom in constituent elements thereof.
  • the photopolymerization initiator has constituent elements composed of only C, H, and O, or constituent elements composed of only C, H, P, and O.
  • An amount of the photopolymerization initiator in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the amount of the photopolymerization initiator is preferably from 0.1% by mass to 10% by mass, more preferably from 0.1% by mass to 5% by mass, and particularly preferably from 1% by mass to 5% by mass, relative to a non-volatile component of the active energy ray curable resin composition.
  • the solvent is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples of the solvent include organic solvents.
  • organic solvents examples include aromatic-based solvents, alcohol-based solvents, ester-based solvents, ketone-based solvents, glycol ether-based solvents, glycol ether ester-based solvents, chlorine-based solvents, ether-based solvents, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, and dimethylacetamide.
  • the solvent is preferably a solvent having a boiling point of 80° C. or higher.
  • Examples of the solvent having a boiling point of 80° C. or higher include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1,3-butanediol, 1,4-butanediol, 2-ethyl-1-hexanol, n-propyl acetate, isopropyl acetate, butyl acetate, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, diacetone alcohol, propylene glycol monomethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, 1,4-dioxane, methyl carbitol, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, and butyl carbitol acetate.
  • An amount of the solvent in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the active energy ray curable resin composition is cured by radiation of active energy rays.
  • the active energy rays are not particularly limited and may be appropriately selected depending on the intended purpose. Examples of the active energy rays include electron beams, UV rays, infrared rays, laser beams, visible rays, ionizing radiation (X rays, ⁇ rays, ß rays, ⁇ rays, etc.), microwaves, and high-frequency waves.
  • FIG. 2 is a schematic cross-sectional view illustrating one example of the laminate of the present invention.
  • the laminate of FIG. 2 includes a substrate 11 , a primer layer 12 , and a functional layer 13 .
  • the active energy ray curable resin composition of the present invention includes a surfactant, and may further include other components, such as urethane (meth)acrylate, a photopolymerization initiator, and a solvent, according to the necessity.
  • the active energy ray curable resin composition is used in formation of the primer layer of the laminate of the present invention.
  • the details and preferable embodiments of the components of the active energy ray curable resin composition are identical to the details and preferable embodiments of the components of the active energy ray curable resin composition in the description of the primer layer.
  • the method for manufacturing a laminate of the present invention includes at least a primer layer-forming step, preferably further includes a functional layer-forming step, and may further include other steps according to the necessity.
  • the method for manufacturing the laminate is a preferable manufacturing method of the laminate of the present invention.
  • primer layer-forming step examples include a step including applying an active energy ray curable resin composition for forming a primer layer on the substrate and curing the active energy ray curable resin composition to form the primer layer.
  • the details and preferable embodiments of the components of the active energy ray curable resin composition for forming a primer layer are identical to the details and preferable embodiments of the components of the active energy ray curable resin composition in the description of the primer layer of the laminate.
  • Examples of the functional layer-forming step include a step including irradiating the active energy ray curable resin composition for forming a functional layer disposed on the primer layer with ultraviolet rays in an atmosphere having an oxygen concentration of less than 1% by volume to form the functional layer.
  • the details and preferable embodiments of the active energy ray curable resin composition for forming a functional layer are identical to the details and preferable embodiments of the active energy ray curable resin composition in the description of the functional layer of the laminate.
  • Excellent curability is obtained by performing ultraviolet ray irradiation in an atmosphere having an oxygen concentration of less than 1% by volume when the functional layer is formed. As a result, a functional layer having a low coefficient of dynamic friction and a high contact angle can be obtained.
  • Examples of the atmosphere having an oxygen concentration of less than 1% by volume include an inert gas atmosphere, such as a nitrogen atmosphere.
  • the product of the present invention includes the laminate of the present invention on a surface thereof.
  • the product may further include other members according to the necessity.
  • the product is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples of the product include window materials (e.g., glass windows, refrigerating/freezing display cases, and windows for automobiles), mirrors for bathrooms, mirrors (e.g., wing mirrors of automobiles), floors and walls of bathrooms, surfaces of solar battery panels, or security surveillance cameras.
  • the product is preferable a mirror, and particularly preferably a mirror for bathrooms or for washstands.
  • the product of FIG. 3 includes a substrate 11 , a primer layer 12 , and a functional layer 13 disposed in this order.
  • the product further includes, on an opposite side of the substrate 11 to the side where the primer layer 12 is disposed, a metal layer 14 and a back protective layer 15 disposed in this order.
  • the substrate 11 is soda lime silica glass produced by a float method etc.
  • a metal layer 14 is formed by a silver mirror reaction, a catalyzer-accelerator method, a sensitizer-activator method, or a vacuum vapor deposition method.
  • a combination of the substrate 11 and the metal layer 14 may not be the above-mentioned combination.
  • the combination may be a glass mirror where multiple layers of a dielectric material are formed by a vacuum vapor deposition method or a sol gel method, a plastic mirror of polycarbonate, polyethylene terephthalate, etc., or a metal mirror of stainless steel, bronze, etc.
  • the back protective layer 15 is disposed to be next to the metal layer 14 for the purpose of preventing corrosion or deterioration of the metal layer 14 .
  • the back protective layer 15 one layer thereof may be disposed, or two or more layers thereof may be disposed.
  • a material of the back protective layer 15 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples of the material thereof include metals (e.g., copper) and resins (e.g., an epoxy resin, an unsaturated polyester resin, a fluororesin, an acrylic resin, an urethane resin, a melamine resin, and a silicone resin).
  • an image of a wire mesh is preferably not distorted when the wire mesh having an opening size of 1 cm is placed at a position that is 1 m away from a surface of the mirror in the normal direction relative to the surface of the mirror, and the image of the wire mesh appeared in the mirror is visually evaluated.
  • the laminate may be formed on part of a surface of the product, or on an entire surface of the product.
  • An average thickness of the functional layer and an average thickness of the primer layer were measured by observing a cross-section of the laminate under field emission scanning electron microscope S-4700 (product name, available from Hitachi High-Technologies Corporation). The thickness was measured at 5 points outside the edge portion and an average value of the measured values was determined as an average thickness.
  • a cross-section profile of a surface of the edge portion of the laminate was measured by means of Stylus Surface Profilometer P-15 available from KLA-Tencor under the following measuring conditions.
  • a wire mesh having an opening size of 1 cm was placed at a position that was 50 cm or 1 m away from a surface of the mirror in the normal direction, and an image of the wire mesh appeared in the mirror was visually evaluated based on the following evaluation criteria.
  • a pure water contact angle was measured using a contact angle meter, PCA-1 (available from Kyowa Interface Science Co., Ltd.) under the following conditions. Distilled water was placed in a plastic syringe. TO the tip of the syringe, stainless steel needle was attached. The distilled water was allowed to drip on an evaluation surface (surface of the functional layer).
  • the contact angle 5 seconds after dripping of water was measured at randomly selected 10 points on the surface of the functional layer, and the average value thereof was determined as the pure water contact angle.
  • a hexadecane contact angle was measured using a contact angle meter, PCA-1 (available from Kyowa Interface Science Co., Ltd.) under the following conditions. Hexadecane was placed in a plastic syringe. To the tip of the syringe, a stainless steel needle was attached. The hexadecane was allowed to drip on an evaluation surface (surface of the functional layer).
  • Amount of hexadecane to be dripped 1 ⁇ L
  • the contact angle 20 seconds after dripping of hexadecane was measured at randomly selected 10 points on the surface of the functional layer, and the average value thereof was determined as the hexadecane contact angle.
  • a coefficient of dynamic friction was measured using Triboster TS501 (product name, available from Kyowa Interface Science Co., Ltd.).
  • BEMCOT registered trademark
  • M-3II product name, available from Asahi Kasei Corporation
  • the coefficient of dynamic friction was measured at randomly selected 12 points at a measuring load of 50 g/cm 2 , a measuring rate of 1.7 mm/s, and a measuring distance of 20 mm, and the average value thereof was determined as the coefficient of dynamic friction.
  • test piece was left to stand in a normal temperature environment for 2 hours, followed by exposing to an environment of 35° C. and 85% RH. A surface of the test piece was visually observed and an anti-fogging property was evaluated based on the following criteria.
  • Very good The area having poor visibility due to fogging and droplets was 30% or less 15 minutes after the test.
  • a container was filled up to about a half the depth thereof with water.
  • the water was heated by a heater ( 1 ) and the temperature of the water ( 2 ) was maintained at 55° C., and the temperature of the air ( 3 ) in the upper space inside the container was maintained at 35° C.
  • the laminate (sample ( 4 )) was arranged in the container in a manner that the laminate was not to be in contact with water (warm water ( 2 )) ( FIG. 4A ). Then, warm water ( 5 ) of about 40° C. was splashed over the functional layer of the laminate (sample ( 4 )) ( FIG. 4B ). Thereafter, the sample was returned to the state of FIG. 4A , and 10 minutes later, cloudiness of the laminate was visually observed. The result was evaluated based on the following evaluation criteria. Note that, in FIG. 4A , “6” is a lid.
  • a surface of the functional layer was stained with Sharpie PROFESSIONAL (product name, black oil-based ink pen, available from Newell Rubbermaid). Thereafter, the stain was wiped with a piece of tissue paper (Elleair, available from DAIO PAPER CORPORATION) 10 times in circle motions. The surface was visually observed and evaluated based on the following criteria.
  • a melamine sponge (product name: Gekiochi-kun) was wet with tap water and then was placed on a surface of the functional layer. After sliding the sponge back and forth 10,000 times (sliding stroke: 3 cm, sliding speed: 6 cm/s) at a load of 300 gf/cm 2 , scratch resistance was evaluated based on the following evaluation criteria.
  • a piece of cloth wet with acetone was placed on a surface of the functional layer for 10 minutes. Thereafter, chemical resistance was evaluated based on the following evaluation criteria.
  • Pencil hardness was measured according to JIS K 5600-5-4.
  • a mirror (a mirror in which a film of silver was formed on float plate glass, average thickness: 5 mm) was used as a substrate.
  • the following resin composition for forming a primer layer was applied onto the mirror serving as the substrate in a manner that an average thickness after drying and curing was to be 2 ⁇ m. After the application, the resin composition was dried for 3 minutes in an oven of 80° C. Ultraviolet ray irradiation was performed using a high-pressure mercury lamp in an air atmosphere at a radiation dose of 500 mJ/cm 2 , to thereby obtain a primer layer.
  • an active energy ray curable resin composition having the following composition was applied onto the primer layer in a manner that an average thickness after drying and curing was to be 35 ⁇ m. After the application, the resin composition was dried for 2 minutes in an oven of 80° C. Ultraviolet ray irradiation was performed using a metal halide lamp in a nitrogen atmosphere at a radiation dose of 500 mJ/cm 2 to cure an anti-fogging and anti-fouling coating layer (functional layer), to thereby obtain an anti-fogging and anti-fouling laminate.
  • An anti-fogging and anti-fouling laminate was obtained in the same manner as in Example 1, except that an anti-fogging and anti-fouling coating layer (functional layer) was formed using an active energy ray curable resin composition having the following composition.
  • the obtained anti-fogging and anti-fouling laminate was evaluated in the same manner as in Example 1. The results are presented in Table 3-1.
  • An anti-fogging and anti-fouling laminate was obtained in the same manner as in Example 1, except that a primer layer was formed using an active energy ray curable resin composition having the following composition and the average thickness of the anti-fogging and anti-fouling coating layer (functional layer) was changed to 45 ⁇ m.
  • the obtained anti-fogging and anti-fouling laminate was evaluated in the same manner as in Example 1. The results are presented in Table 3-1.
  • An anti-fogging and anti-fouling laminate was obtained in the same manner as in Example 1, except that the average thickness of the anti-fogging and anti-fouling coating layer was changed to 45 ⁇ m.
  • the obtained anti-fogging and anti-fouling laminate was evaluated in the same manner as in Example 1. The results are presented in Table 3-1.
  • An anti-fogging and anti-fouling laminate was obtained in the same manner as in Example 1, except that the primer layer was formed using an active energy ray curable resin composition having the following composition.
  • the obtained anti-fogging and anti-fouling laminate was evaluated in the same manner as in Example 1. The results are presented in Table 3-1.
  • An anti-fogging and anti-fouling laminate was obtained in the same manner as in Example 1, except that the primer layer was formed using an active energy ray curable resin composition having the following composition.
  • the obtained anti-fogging and anti-fouling laminate was evaluated in the same manner as in Example 1. The results are presented in Table 3-1.
  • Each anti-fogging and anti-fouling laminate was obtained in the same manner as in Example 1, except that the resin composition for forming a primer layer, the resin composition for forming a functional layer, the average thickness of the primer layer, and the average thickness of the functional layer were changed to the resin composition for forming a primer layer, resin composition for forming a functional layer, average thickness of the primer layer, and average thickness of the functional layer presented in Table 2-2.
  • a unit for the formulated amount in Tables 2-1 and 2-2 is part(s) by mass.
  • Examples 1 to 9 distortion of the image at the edge of the mirror was minor compared to Comparative Examples.
  • distortion of the image at the edge of the mirror was not particularly noticed in Example 2 because the height (h) of the projected portion was 5.5 mm or less, the width (w) of the projected portion was 6.0 mm or less, and the length (l) between the edge side and the apex was 3.0 mm or less.
  • the laminate of the present invention can be used for window materials (e.g., glass windows, refrigerating/freezing display cases, and windows for automobiles), mirrors used near water (e.g., bathroom mirrors and washstand mirrors), mirrors (e.g., wing mirrors of automobiles), floors and walls of bathrooms, surfaces of solar battery panels, or security surveillance cameras.
  • the laminate of the present invention can be more preferably used for a mirror for bathrooms and washstands.

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JP6637243B2 (ja) * 2015-03-09 2020-01-29 デクセリアルズ株式会社 防曇防汚積層体、及びその製造方法、物品、及びその製造方法、並びに防汚方法
JP6568294B2 (ja) * 2018-02-21 2019-08-28 デクセリアルズ株式会社 活性エネルギー線硬化性樹脂組成物、防曇防汚積層体、及びその製造方法、物品、並びに防曇方法
CN112409915A (zh) * 2020-12-21 2021-02-26 广州市奈森化工有限公司 亲水疏油防雾光固化涂料及其制备方法
JP7004366B1 (ja) 2021-09-08 2022-02-14 株式会社Tbm 印刷用シート及び印刷用シートの製造方法

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